KR20200114463A - A colored photosensitive resin composition, a black column spacer, color filter manufactured by using the composition and display device comprising the composition - Google Patents

Abstract

The present invention relates to: a colored photosensitive resin composition comprising a pigment including a quinoline structure, carbon black and C.I pigment blue 60; a black column spacer and a color filter manufactured therefrom; and a display device including the same. The colored photosensitive resin composition of the present invention has excellent solvent resistance and reliability as a column spacer.

Description

A colored photosensitive resin composition, a black column spacer, color filter manufactured by using the composition and display device comprising the composition}

The present invention relates to a colored photosensitive resin composition, a black column spacer manufactured using the same, a color filter, and an image display device including the same.

Recently, the display industry has undergone a drastic change from CRT to flat panel displays represented by PDP, OLED, and LCD. Among them, a liquid crystal display (LCD) is widely used as an image display device in almost all industries, and its application range is continuously expanding. Therefore, Pigment or dye-based color filters used for color realization in existing liquid crystal display devices are essential. In general, a black matrix is used to absorb external light reflection and improve contrast. Column spacers have been used to maintain the gap.

However, when the black matrix and the column spacer are respectively manufactured and used as described above, the process is complicated, and the configuration of the black matrix has a problem that it is difficult to form a complete black due to the reflected color by reflecting light emitted by the backlight unit. There has been a problem in that the transmittance for a long wavelength decreases. Accordingly, there has been a demand for development of a black column spacer in which a black matrix and a column spacer are integrated into one module due to the demand for simplification of the process.

Relatedly, Korean Patent Laid-Open Publication No. 10-2006-0125993 discloses a technology that can be used as a black column spacer, but in the case of the above technology, there is a problem in that the blue taste and optical density in the transmitted color are lowered, and all wavelengths The problem of lowering the optical density occurred due to absorption in the region.

Accordingly, the present invention has reached the present invention to provide a colored photosensitive resin composition that can be used excellently for a black column spacer in order to solve the above problems.

Korean Publication No. 10-2006-0125993

In order to solve the above problems, the present invention has excellent reliability such as solvent resistance for the role of a column spacer, and has excellent optical density, particularly, excellent optical density in the 380 to 790 nm wavelength region. It is an object of the present invention to provide a possible colored photosensitive resin composition.

In addition, an object of the present invention is to provide a black column spacer capable of excellently forming a gap between glass substrates.

Further, an object of the present invention is to provide a color filter and an image display device having excellent luminance and color reproducibility.

The present invention is a pigment comprising a quinoline structure; Carbon black; And it provides a colored photosensitive resin composition comprising the C.I pigment blue 60.

In addition, the present invention provides a black column spacer made of the above-described colored photosensitive resin composition.

In addition, the present invention is a color filter made of the above-described colored photosensitive resin composition.

In addition, the present invention provides an image display device including the black column spacer described above.

The colored photosensitive resin composition of the present invention has excellent solvent resistance and reliability as a column spacer, has excellent optical density as a black matrix, can form a transmittance for a long wavelength, and exhibits an effect that the transmitted color is blue.

In addition, the present invention has the effect of being able to provide excellent color reproduction by being manufactured with the colored photosensitive resin composition, and providing a black column spacer, a color filter, and a display device including the same, which can be manufactured with excellent efficiency.

The present invention relates to a colored photosensitive resin composition for manufacturing a black column spacer capable of simultaneously serving as a column spacer and a black matrix in a display device by including a pigment including a quinoline structure, carbon black, and CI pigment blue 60. .

coloring agent

The present invention is a pigment comprising a quinoline structure as a colorant; Carbon black; And C.I pigment blue 60 may be included. In the case of including the pigment, it is preferable in that the black column spacer can have a blue color in the transmission color when the black column spacer is formed, and excellent optical density can be formed in the wavelength range of 380 to 780 nm.

The pigment including the quinoline structure may be more preferable in that it may have excellent optical density to include at least one selected from the group consisting of C.I pigment yellow 139 and C.I pigment yellow 185. In addition, the present invention may further include C.I pigment violet 29 as a colorant.

The colored photosensitive resin composition may include 3 to 6% by weight of a pigment including a quinoline structure, 5 to 6% by weight of carbon black, and 16 to 25% by weight of C.I pigment blue 60 based on the total weight of the solid content.

Carbon black is a pigment that has the most influence on unit OD, and if it is included in the above range, it is easy to secure fairness, and it may be preferable in that it can satisfy Near-IR transmittance of 19.0% (@ 3.2um thickness) or more. have.

When the pigment containing the quinoline structure is included in the above range, the average absorbance (@ 401 ~ 500nm) = 1.40, and the average absorbance (@ 401 ~ 500nm) / ⓑ average absorbance (@ 501 ~ 680nm) <1 It is preferable in that the NMP elution reliability can be improved.

When the CI pigment blue 60 is included in the above range, ⓑ average absorbance (@ 501 ~ 680nm) is 1.45 and @ average absorbance (@ 401 ~ 500nm) / ⓑ average absorbance (@ 501 ~ 680nm) <1 It is preferable in that it may not cause the problem of lowering the transmittance of Near-IR to less than 19.0%, and the problem of lowering NMP elution and VHR characteristics.

The present invention may further include 9 to 12% by weight of CI pigment violet 29, and when including CI pigment violet 29 in the above range, ⓐ average absorbance (@ 401 to 500 nm) = 1.40 and ⓑ average absorbance (@ 501 to 680nm) = 1.45 can be satisfied, and NMP reliability and VHR reliability deterioration is preferable in that it may not occur.

In the present invention, "solid content" means a component excluding a solvent in the total composition of the colored photosensitive resin composition.

The present invention may further contain one or more of a photopolymerizable compound, a photopolymerization initiator, a binder resin, a solvent, and an additive.

Photopolymerizable compound

The present invention may further contain a photopolymerizable compound. The photopolymerizable compound is a compound that can be polymerized by the action of a photopolymerization initiator described later, and includes a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethylacrylate, and N-vinylpi And rolidone. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , Bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth)acrylate, and the like. Specific examples of other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di And pentaerythritol hexa(meth)acrylate. Among these, a bifunctional or higher polyfunctional monomer is preferably used.

The photopolymerizable compound may be included in an amount of 0.1 to 30% by weight, preferably 0.5 to 25% by weight, based on the total weight of the solid content in the colored photosensitive composition. When the photopolymerizable compound is contained within the above range, it is preferable because the intensity and smoothness of the pixel portion tend to be improved.

Binder resin

The binder resin generally has reactivity and alkali solubility by the action of light or heat, and acts as a dispersion medium of the coloring material. The binder resin contained in the colored photosensitive resin composition of the present invention acts as a binder resin for a fluorescent dye, and any binder resin soluble in an alkaline developer used in the developing step for manufacturing a color filter may be used.

The binder resin includes, for example, a carboxyl group-containing monomer and a copolymer of another monomer copolymerizable with this monomer. Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids having one or more carboxyl groups in the molecule. have. Here, as an unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc. are mentioned, for example. As an unsaturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc. are mentioned, for example. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, etc. are mentioned. In addition, the unsaturated polyhydric carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl) ), mono phthalic acid (2-acryloyloxyethyl), mono phthalic acid (2-methacryloyloxyethyl), and the like. The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of the dicarboxylic polymer at both ends, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. . These carboxyl group-containing monomers may be used alone or in combination of two or more. Other monomers that can be copolymerized with the carboxyl group-containing monomer include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxy. Toxoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzyl glycidyl ether, m-vinylbenzylglycidyl ether, p- Aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Roxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl

Methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methacrylate Toxictriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate , Dicyclopentadienyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2 -Unsaturated carboxylic acid esters such as hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl, such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethyl methacrylamide; Maleimide, benzylmaleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; And a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. And macromonomers to have. These monomers can be used alone or in combination of two or more. Particularly, bulky monomers such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton as other monomers copolymerizable with the carboxyl group-containing monomer are preferable because they tend to lower the relative dielectric constant value. .

The binder resin of the present invention preferably has an acid value in the range of 20 to 200 (KOH mg/g). When the acid value is in the above range, the solubility in the developer is improved, the non-exposed portion is easily dissolved and the sensitivity is increased, as a result, the pattern of the exposed portion remains during development, thereby improving the film remaining ratio, which is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be usually determined by titration using an aqueous potassium hydroxide solution. In addition, the weight average molecular weight in terms of polystyrene (hereinafter, simply referred to as'weight average molecular weight') measured by gel permeation chromatography (GPC; tetrahydrofuran as an elution solvent) is 3,000 to 200,000, preferably 5,000 to 100,000. In the resin is preferred. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution tends to be improved, which is preferable.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the binder resin is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. A molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1.5 to 6.0 because developability is excellent.

The content of the binder resin of the present invention is usually in the range of 5 to 85% by mass, preferably 10 to 70% by mass, based on the solid content in the colored photosensitive resin composition. When the content of the binder resin is included in the above range, the solubility in the developer is sufficient to suppress the occurrence of development residue on the substrate in the non-pixel portion, and the problem of film reduction in the pixel portion of the exposed portion during development can be solved. It is preferable because there is a tendency that the omission of non-pixel portions tends to be good.

Photoinitiator

The photoinitiator used in the present invention may include at least one selected from the group consisting of benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, triazine-based compounds, and acetophenone-based compounds. Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1-[4-( 2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propane-1 -One oligomer, etc. are mentioned, Preferably, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one etc. are mentioned. Among the photoinitiators, photoinitiators other than acetophenone-based may include active radical generators, sensitizers, and acid generators that generate active radicals by irradiation with light. Examples of the active radical generators include benzoin-based photopolymerization initiators. Compounds, benzophenone compounds, thioxanthone compounds, and triazine compounds. Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzo isobutyl ether. As a benzophenone compound, for example, benzophenone, o-benzoyl benzoate methyl, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra( t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned. As a thioxanthone compound, for example, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro- 4-propoxy oxanthone, etc. are mentioned. As a triazine-based compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) -6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-methylphenyl)ethenyl]-1,3,5-triazine,2,4-bis(trichloromethyl)-6-[2-(3,4dimethoxyphenyl)ethenyl]-1,3,5 -Triazine, etc. are mentioned. Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2,-bis(o-chlorophenyl)-4,4', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene Compounds and the like can be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylsulfonium p-toluenesulfonium Nate, 4-acetoxyphenylmethylbenzylsulfoniumhexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumhexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts, such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned. In addition, among the above compounds as an active radical generator, some compounds that generate an acid at the same time as the active radical are used. For example, a triazine-based photopolymerization initiator is also used as an acid generator.

The content of the photoinitiator used in the colored photosensitive resin composition according to the present invention is 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total solid content. If it is in the above range, the colored photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed using the composition and the smoothness on the surface of the pixel portion tends to be favorable, which is preferable.

Furthermore, the present invention may further include a photopolymerization initiation aid if necessary. The photopolymerization initiation aid is sometimes used in combination with a photoinitiator, and is a compound used to accelerate polymerization of a photopolymerizable compound in which polymerization has been initiated by a photoinitiator. As a photopolymerization initiation aid, an amine compound, an alkoxyanthracene compound, a thioxanthone compound, etc. are mentioned.

Examples of amine compounds include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylamino benzoic acid. Ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzphenone (common name, Michler's ketone), 4,4'-bis(diethyl Amino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, and the like. Among them, 4,4'-bis (diethylamino) benzophenone is preferable. As an alkoxyanthracene compound, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene And the like. As a thioxanthone-based compound, for example, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro- 4-propoxy oxanthone, etc. are mentioned. Even if these photoinitiators (D) are used alone or in combination of a plurality of them, there is no problem. Moreover, what is marketed can be used as a photoinitiation aid, and as a commercially available photoinitiation aid, a brand name "EAB-F" [manufacturer: Hodogaya Chemical Industry Co., Ltd.] etc. are mentioned, for example.

In the case of using these photopolymerization initiators, the amount of the photoinitiator is generally 10 mol or less, preferably 0.01 to 5 mol per 1 mol of the photoinitiator. If it is in the above range, the sensitivity of the colored photosensitive resin composition is further increased, and the productivity of the color filter formed using this composition tends to be improved, which is preferable.

solvent

The solvent contained in the colored photosensitive resin composition of the present invention is not particularly limited, and various organic solvents used in the field of the colored photosensitive resin composition can be used. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene. Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol Alkylene glycol alkyl ether acetates such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, methyl ethyl ketone, acetone , Methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3-methoxy Esters such as methyl propionate, and cyclic esters such as γ-butyrolactone. Among the above solvents, organic solvents having a boiling point of 100° C. to 200° C. are preferably mentioned in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy Esters such as ethyl propionate and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy ethylpropionate, 3- Methyl methoxypropionate, and the like. These solvents can be used alone or in combination of two or more.

The content of the solvent in the colored photosensitive resin composition of the present invention is 45 to 90% by weight, preferably 45 to 85% by weight, based on the total amount of the colored photosensitive resin composition containing the same. If the solvent content is within the above reference range, the coating property tends to be good when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or inkjet. desirable.

additive

The present invention may further include additives as needed.

In the present invention, the additive may include at least one selected from the group consisting of a dispersant (surfactant), a filler, a hardener, an antioxidant and an adhesion enhancer.

The dispersant is added for deaggregation and stability maintenance of quantum dots and scattering particles, and may be used without limitation, which is generally used in the art. Specific examples of the dispersant include cationic, anionic, nonionic, and amphoteric And surfactants such as polyester-based and polyamine-based, and these can be used alone or in combination of two or more.

Specific examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes and polyethyleneimines are listed. have.

In addition, the dispersant preferably includes an acrylate-based dispersant (hereinafter, an acrylate-based dispersant) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). Commercially available products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and the acrylate-based dispersants are used alone or in combination of two or more. I can.

In addition to the acrylate-based dispersant, the dispersant may be a resin type dispersant. As the dispersant of the other resin type, a known dispersant of a resin type, in particular, a polycarboxylic acid ester typified by polyurethane and polyacrylate, an unsaturated polyamide, a polycarboxylic acid, a (partially) amine salt of a polycarboxylic acid , Ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free carboxyl groups An oily dispersant such as an amide or a salt thereof formed by reaction of a polyester having a poly(lower alkyleneimine); Water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylate; Adducts of ethylene oxide/propylene oxide; And phosphate esters.

Commercially available products of the above other resin type dispersants include cationic resin dispersants, for example, BYK Chemie's brand names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK -164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF's brand names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Kawaken Fine Chemical's trade names: Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto's brand names: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; Kyoeisha Chemical Co., Ltd. trade names: FLORENE DOPA-17HF, Florene DOPA-15BHF, Floren DOPA-33, Florene DOPA-44, and the like.

In addition to the above acrylate-based dispersants, other resin-type dispersants may be used alone or in combination of two or more, or may be used in combination with an acrylate-based dispersant.

The dispersant may be included in an amount of 0.1 to 50 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the solid content of the colored photosensitive resin composition. When the dispersant is contained within the above range, it is preferable because the gelation process is easy after dispersing the colorant.

Specific examples of the surfactants include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants, and these may be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, In addition to polyethyleneimines, brand names are F-554 (manufactured by DIC Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyei Chemical Co., Ltd.), Ftop (manufactured by Tochem Products). , MegaPak (manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.), Florade (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Saffron (above, manufactured by Asahi Glass Co., Ltd.), Sor Spas (manufactured by Geneva Co., Ltd.) ), EFKA (manufactured by EFKACHEMICALS), PB821 (manufactured by Ajinomoto Co., Ltd.), and the like.

Glass, silica, alumina, etc. may be used as the filler, and specific examples of the other polymer compounds include curable resins such as epoxy resin and maleimide resin; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The curing agent is used to increase deep curing and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound. Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, Glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene (co ) Polymer epoxidation, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc. are mentioned. Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane. The curing agent may be used in combination with a curing agent and a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The carboxylic anhydrides may be commercially available as an epoxy resin curing agent. As the epoxy resin curing agent, for example, a brand name (Adeka Hadona EH-700) (manufactured by Adeka Industries Co., Ltd.), a brand name (Rikashido HH) (manufactured by Shin Nippon Ewha Corporation), and a brand name (MH-700) ( Shin Japan Ewha Co., Ltd.) and the like. The curing agent exemplified above may be used alone or in combination of two or more.

As the adhesion enhancer, a silane-based compound is preferable, and specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)- 3-Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-gly Cydoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxy Propyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, etc. are mentioned.

The above additives may be appropriately added and used by those skilled in the art within a range that does not impair the effects of the present invention. For example, the additive may be used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on the total 100 parts by weight of the colored photosensitive composition, but is not limited thereto.

<Black column spacer>

In addition, the present invention provides a black column spacer made of the colored photosensitive resin composition.

<Color filter>

The present invention can provide a color filter including the black column spacer.

<Display device>

The display device according to the present invention includes the above-described light conversion laminated substrate. Specifically, the image display device is a liquid crystal display (liquid crystal display; LCD), an organic EL display (including organic EL display, OLED and QLED), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone. , Display devices for digital cameras, display devices for car navigation, and the like, and color display devices are particularly suitable.

The display device may further include a configuration known to a person skilled in the art, except for the light conversion laminated substrate.

Hereinafter, examples for the practice of the present invention will be described in detail. However, the implementation of the present invention is not limited thereto, and may be modified in other forms.

The "%" and parts indicating the content hereinafter are based on weight unless otherwise noted.

Synthesis Example: Preparation of binder resin A

Into a 1-liter separate flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, 277 g of methoxybutyl acetate was added, the temperature was raised to 80°C, and then 3,4-epoxytricyclo[5.2.1.02 ,6] a mixture of decane-9-ylacrylate and 3,4-epoxytricyclo[5.2.1.02,6]decane-8-ylacrylate [50:50 (molar ratio)] 301 g, methacrylic acid 49 g, And a mixed solution in which 23 g of azobisdimethylvaleronitrile was dissolved in 350 g of methoxybutyl acetate was added dropwise over 5 hours, and further aged for 3 hours to obtain a copolymer solution A [solid content (NV) 35.0 wt%]. The acid value (dry) of the obtained copolymer was 69.8 KOH mg/g, the weight average molecular weight (Mw) was 12300, and the dispersion degree (Mw/Mn) was 2.1.

Preparation Example: Preparation of a colored dispersion

As a pigment, C.I. Pigment Violet 29 (PV29) 15.0 parts by weight, the dispersion resin is 3 parts by weight (in terms of solid content) [solid content (NV) 35.0 wt%] as a dispersion resin using the binder resin A prepared in Synthesis Example, the dispersant is an acrylic polymer dispersant (DISPERBYK -2000) A composition consisting of 7 parts by weight (in terms of solid content) [solid content (NV) 40.0% by weight] and 75 parts by weight of propylene glycol monomethyl ether acetate as a solvent and a rigid milling medium (zirconia beads) having an average particle diameter of 0.1 mm were added to 50 After mixing and adding at a weight ratio of :50, 4 kinds of pigments were co-dispersed with a bead mill for 4-6 hours to prepare a colored dispersion (B-1).

C.I. in the same manner as in the above colored dispersion preparation (B-1). Instead of Pigment Violet 29 (PV29), C.I. Pigment Yellow 139 (PY139), C.I. Pigment Blue 60 (PB60), C.I. Pigment Orange 64 (PO64), C.I. Pigment Blue 15:6 (PB15:6), C.I. Pigment violet 23 (PV23) and carbon black (CB) were respectively changed and introduced, and colored dispersions 2 (B-2) to 7 (B-7) were prepared according to the composition of [Table 1].

[Table 1]

Examples and Comparative Examples

Black photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were prepared so that a total of 100 g including the pigment dispersion prepared in [Table 1] with the composition shown in [Table 2] below.

[Table 2]

Experimental example

Manufacture of substrate (manufacture of color filter color conversion layer (color conversion pixel; Glass substrate))

A 5cmX5cm glass substrate (Corning) was washed with a neutral detergent and water, and then dried. Each of the black photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 3 on the glass substrate was spin-coated so that the final film thickness was 3.0 μm, and pre-baked at 80 to 120°C to 1 to 2 The solvent was removed by drying for a minute. Then, a pattern was formed by exposure with an exposure amount of 25 to 35 mJ/cm ^2, and the non-exposed portion was removed using an alkaline aqueous solution. Then, after firing at 200 to 250°C for 10 to 30 minutes, a black substrate was prepared.

Experimental Example 1 Measurement of absorbance

Using the coating film prepared by the above method, absorbance at a visible wavelength was measured using a shimadzu UV-2600 device. The film thickness of the final fabricated substrate was prepared (Dektak) with a film thickness before/after 1 μm, and the absorbance (@1 μm) was measured, and the evaluation criteria are shown in Table 3 and the results are shown in Table 4.

Experimental Example 2 Measurement of Near-IR T

Using the coating film prepared by the above method, absorbance at a visible wavelength was measured using a shimadzu UV-2600 device. The film thickness of the final fabricated substrate was prepared with a film thickness before/after 3.2 μm, and the transmittance (@3.2 μm) was measured.

Experimental Example 3 NMP elution degree measurement

Reliability was judged by measuring the solvent resistance using the prepared coating film.

The solvent resistance measurement was performed by immersing the coating film (3*3) in an 18g NMP solution at 100°C for 60 minutes, extracting the NMP solvent, and measuring the absorbance at the visible wavelength of the NMP solvent after immersion using a shimadzu UV-2600 instrument. . After immersion in the color filter, the peak absorbance of the NMP solvent (sum of absorbance at 400 nm to 700 nm, measurement was measured at 1 nm intervals).

Experimental Example 4 VHR characteristic measurement

The coating film is scraped, doped 3% on the liquid crystal, eluted at 100° C./3 hours, filtered at 0.2 μm, and injected into the VHR cell. This cell was measured under the following measurement conditions, and the evaluation criteria are shown in Table 3 and the results are shown in Table 4.

-Measurement equipment: Toyo, Model 6254

-Measurement conditions: 1V, 250us, 60Hz

[Table 3]

[Table 4]

Claims (10)

Pigments containing a quinoline structure; Carbon black; And CI pigment blue 60 colored photosensitive resin composition comprising a.
The method according to claim 1,
The pigment comprising the quinoline structure is at least one selected from the group consisting of CI pigment yellow 139 and CI pigment yellow 185, a colored photosensitive resin composition.
The method according to claim 1,
The colored photosensitive resin composition is a colored photosensitive resin composition for forming a black column spacer.
The method according to claim 1,
The colored photosensitive resin composition will further comprise CI pigment violet 29, colored photosensitive resin composition.
The method according to claim 1,
The colored photosensitive resin composition further comprises at least one selected from the group consisting of a photopolymerizable compound, a photopolymerization initiator, a binder resin, a solvent and an additive.
The method according to claim 1,
The colored photosensitive resin composition comprises 3 to 6% by weight of a pigment including a quinoline structure, 5 to 6% by weight of carbon black, and 16 to 25% by weight of CI pigment blue 60 based on the total weight of the solid content.
The colored photosensitive resin composition of claim 4, wherein the colored photosensitive resin composition further comprises 9 to 12% by weight of CI pigment violet 29 based on the total weight of the solid content.
A black column spacer made of the colored photosensitive resin composition of any one of claims 1 to 7.
A color filter made of the colored photosensitive resin composition of any one of claims 1 to 7.
An image display device comprising the black column spacer of claim 8.